Background: This study aimed to assess the association of 18F-Fluorodeoxyglucose positron-emission-tomography (18F-FDG/PET) and DWI imaging parameters from a primary tumor and their correlations with clinicopathological factors. Methods: We retrospectively analyzed primary tumors in 71 patients with proven HNC. Primary tumor radiological parameters: DWI and FDG, as well as pathological characteristics were analyzed. Spearman correlation coefficient was used to assess the correlation between DWI and FDG parameters, ANOVA or Kruskal–Wallis, independent sample t-test, Mann–Whitney test, and multiple regression were performed on the clinicopathological features that may affect the 18F- FDG and apparent-diffusion coefficient (ADC) of the tumor. Results: No significant correlations were observed between DWI and any of the 18F-FDG parameters (p > 0.05). SUVmax correlated with N-stages (p = 0.023), TLG and MTV correlated with T-stages (p = 0.006 and p = 0.001), and ADC correlated with tumor grades (p = 0.05). SUVmax was able to differentiate between N+ and N− groups (p = 0.004). Conclusions: Our results revealed a non-significant correlation between the FDG-PET and ADC-MR parameters. FDG-PET-based glucose metabolic and DWI-MR-derived cellularity data may represent different biological aspects of HNC.